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EP2297061B1 - Mixture, in particular construction material mixture containing furnace slag - Google Patents

Mixture, in particular construction material mixture containing furnace slag Download PDF

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Publication number
EP2297061B1
EP2297061B1 EP09753796A EP09753796A EP2297061B1 EP 2297061 B1 EP2297061 B1 EP 2297061B1 EP 09753796 A EP09753796 A EP 09753796A EP 09753796 A EP09753796 A EP 09753796A EP 2297061 B1 EP2297061 B1 EP 2297061B1
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EP
European Patent Office
Prior art keywords
building material
binder system
zinc
alkali metal
material binder
Prior art date
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EP09753796A
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German (de)
French (fr)
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EP2297061A1 (en
Inventor
Florian Ellenrieder
Katja Voland
Uwe Gehrig
Samuele Beraldo
Joachim Riedmiller
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Construction Research and Technology GmbH
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Construction Research and Technology GmbH
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Priority to EP09753796A priority Critical patent/EP2297061B1/en
Priority to PL09753796T priority patent/PL2297061T3/en
Publication of EP2297061A1 publication Critical patent/EP2297061A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/08—Slag cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26—Silicates of the alkali metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482—Coating or impregnation materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00663—Uses not provided for elsewhere in C04B2111/00 as filling material for cavities or the like
    • C04B2111/00672—Pointing or jointing materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/2038—Resistance against physical degradation
    • C04B2111/2076—Discolouring resistant materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the present invention relates to building material binder systems containing granulated slag as a first binder and microsilica and / or metakaolin as a second binder, zinc salts wherein the zinc salts have from 0 to 8 carbon atoms in their structure, and an alkali metal compound as activator. Furthermore, the invention relates joint grout or coatings containing the building material binder systems according to the invention, and the use of zinc salts in building material binder systems based on granulated sludge to prevent discoloration.
  • Inorganic binder systems based on reactive water-insoluble silica based oxides in conjunction with alumina which cure in aqueous alkaline medium are well known. Such binder systems are also called geopolymers and are in EP 0 026 687 . EP 0 153 097 B1 and WO 82/00816 described.
  • Metakaolin, slag, fly ash, activated clay or a mixture thereof can be used as a reactive oxide mixture.
  • the alkaline medium for activating the binder usually consists of aqueous solutions of alkali metal carbonates, fluorides and in particular alkali metal hydroxide and / or soluble water glass.
  • the hardened binders have a high mechanical and chemical resistance. Compared to cement, these are cheaper, more durable and have a more favorable CO 2 emission balance.
  • Slag sand is a reactive slag from the blast furnace process.
  • Binder systems based on slag sand as the main component of the reactive solid component in conjunction with an aqueous solution of an alkali hydroxide and / or water glass in construction by mixing with fillers (quartz sand with appropriate grain size) and additives as mortar or Concretes are used.
  • fillers quartz sand with appropriate grain size
  • additives as mortar or Concretes
  • Such binder systems and mortars are in DE 3 133 503 .
  • JP 4 012 043 and JP 11 079 822 described.
  • EP 1 236 702 A1 describes a water glass-containing building material mixture for the production of chemical-resistant mortars based on a latent hydraulic binder, water glass and metal salt as a control agent.
  • Granulated blastfurnace slag can also be used as a latent hydraulic component.
  • metal salt alkali salts are called and used.
  • EP 0 457 516 A1 describes refractory, waterproof, acid-resistant binders of alkali metal silicates such as microsilica.
  • alkali metal silicates such as microsilica.
  • various metal oxides, including zinc oxide are used as setting accelerator.
  • the CH 629 246 A5 describes a method for adhering a metal foil to a mineral fiber board, wherein an adhesive of water glass, clay mineral substances and, inter alia, oxides of alkaline earths or zinc are used.
  • compositions for coloring concrete containing at least one derivative of stearic acid, a polymer and a pigment are described.
  • Stearinklad also zinc stearate is listed.
  • the stearic acid derivatives serve as water repellents to prevent efflorescence on the surface of cementitious concretes.
  • the document does not mention the effects of zinc-containing compounds as agents for preventing discoloration in slag-containing binder systems.
  • US 5 073 198 describes an improved process for making a building material comprising slag activated with Portland cement activator, an acidic component and a basic component.
  • the acidic component is phosphate (e), the basic component magnesium oxide in combination with oxides such as zinc oxide.
  • the presence of Portland cement increases the mechanical strength of the building material.
  • a disadvantage of the known building material mixtures based on alkaline activated slag sand is that it may cause discoloration when the system hardens. In particular, in areas where the access of atmospheric oxygen is hindered show increasingly dark discoloration. It is assumed that these discolorations are caused by sulfur-containing compounds in the oxidation state -2. The mortars and concretes produced with this binder system thus do not show a uniform color image. In particular, when using such binder systems in visible coatings and grout, these discolorations can lead to unacceptable results.
  • the task was therefore to provide a building material binder system based on granulated slag, which shows no discoloration after application and curing.
  • the present invention accordingly provides a building material binder system containing granulated slag as a first binder and microsilica and / or metakaolin as a second binder, characterized in that it contains zinc salt, wherein the zinc salt has from 0 to 8 carbon atoms, and an alkali metal compound as activator.
  • zinc salts which have no carbon atoms in their structure.
  • the building material binder systems according to the invention have the advantage that they can be used to inexpensively discolor mortar and concretes, in particular joint mortars and coatings for the construction industry.
  • binders can be used as binders in the building-material binder systems according to the invention.
  • latent hydraulic binders and pozzolans are also known by the generic terms latent hydraulic binders and pozzolans.
  • one or more of said binders can be used with granulated blastfurnace slag. Fly ash is especially preferred.
  • Slag sand is granulated blast furnace slag.
  • Finely ground granulated blastfurnace slag is also known as blastfurnace slag.
  • Such products are generally known to the skilled person as a binder.
  • Granulated blastfurnace flour varies in its fineness and particle size distribution, depending on its origin and its form of preparation, whereby the fineness of grinding has an influence on the reactivity of the granulated blastfurnace meal.
  • the blastfurnace slag or blastfurnace sludge can generally be used in a known form for building material mixtures which set by alkaline activation.
  • blast furnace slag which has a Blaine value of greater than 2000 cm 2 / g, particularly preferably greater than 3000 cm 2 / g.
  • blast furnace slag comes into question, which has a Blaine value between 2000 to 10000 cm 2 / g, particularly preferably between 3000 and 5000 cm 2 / g.
  • Particularly preferred according to the present invention is blast furnace slag containing between 30 and 45% by weight of CaO, between 30 and 45% by weight of SiO 2 , between 5 and 15% by weight Al 2 O 3 and between 4 and 17% by weight. - contains% MgO.
  • the building material binder system according to the invention contains as activator preferably pulverulent activator, particularly preferably alkali metal hydroxide, alkali metal silicate, in particular alkaline potassium silicate, alkali metal aluminate, alkali metal carbonate and / or alkali metal sulfates.
  • activator preferably pulverulent activator, particularly preferably alkali metal hydroxide, alkali metal silicate, in particular alkaline potassium silicate, alkali metal aluminate, alkali metal carbonate and / or alkali metal sulfates.
  • alkali metal is sodium, potassium or lithium.
  • the alkali metal silicate may be sodium, potassium or lithium waterglass, preferably potassium silicate glass.
  • the modulus (molar ratio SiO 2 to alkali oxide) of the water glass is preferably less than 4, particularly preferably less than 2. In the case of water glass powder, the modulus is expediently less than 5, preferably between 1 and 4, particularly preferably between 1 and 3.
  • the above-mentioned alkali metal compound as an activator may also be sodium, potassium and lithium hydroxide.
  • the building material binder system according to the invention preferably contains the following components in the following proportions: between 0.001 and 10% by weight of zinc salt, between 5 and 50% by weight of granulated slag, between 5 and 50% by weight of activator, the weight data being based in each case on the total weight of the building material binder system.
  • the zinc salt according to the invention it is possible, provided that the zinc salt has from 0 to 8 carbon atoms in its structure, to use mixtures which are generally known in the mixtures, for example organic (for example zinc salts of organic carboxylic acids) or inorganic zinc salts, preferably those based on Zn 2+ , particularly preferred inorganic zinc salts, in particular inorganic zinc salts, which are soluble in an aqueous alkaline medium.
  • Zinc oxide, zinc fluoride and / or zinc sulfate are preferably used as the zinc salt.
  • Zinc chloride can also be used, but is less desirable because of its chloride content in larger quantities.
  • Zinc oxide is particularly preferably used, which is readily soluble in aqueous alkaline solution.
  • the building material binder system it is particularly preferred to contain from 0.1 to 7% by weight and in particular from 0.5 to 5% by weight of zinc salt.
  • Zinc salts with more than eight carbon atoms per structural unit, such as zinc stearate, have the disadvantage that probably due to their hydrophobic structure, the strength of the building material mixtures are adversely affected. Also, the hardened building material becomes more porous and thus less durable. It is basically possible to use the said zinc salts alone or mixtures of different zinc salts.
  • the zinc salts according to the invention can preferably be mixed into the mixture containing the granulated blastfurnace meal in powder form.
  • the zinc salt is mixed into the powdery granulated slag-containing binder mixture.
  • the zinc salts may be used as a solution in an activator described above. Before mixing the binder with the aqueous activator solution, the zinc salt may preferably be dissolved in the aqueous activator solution.
  • the zinc salt is preferably a ground salt, which preferably has particle sizes with a d 90 value of less than 90 ⁇ m.
  • the rate of dissolution of the zinc salt increases with increasing fineness of fining.
  • the activator described above is preferably pulverulent. This is referred to as a one-component system, which can then be made to harden by the addition of water.
  • the activator serves to accelerate the setting process of the binders.
  • the activator can also be used in the form of a solution.
  • the activator solution is mixed with a mixture of granulated blastfurnace and the other binders, whereupon curing begins.
  • between 0 and 80% by weight, particularly preferably between 30 and 70% by weight of fillers, and optionally between 0 and 15% by weight, of additives differing from the abovementioned components may be present in the building material binder system.
  • the weights are in each case based on the total weight of the building material binder system.
  • the building material binder system according to the invention is preferably used for the production of mortars and concretes.
  • the building material binder system is usually mixed with other components such as fillers, latent hydraulic substances and other additives.
  • the addition of the powdered activator is preferably carried out before the said components are mixed with water, so that a so-called dry mortar is prepared.
  • the activation component is in powder form, preferably as a mixture with the binders and / or sand.
  • an aqueous, preferably alkaline, activating solution may be added to the other powdered components. In this case one speaks then of a two-component binder.
  • Suitable fillers are generally known gravels, sands and / or flours, for example based on quartz, limestone, barite or clays. Also light fillers such as perlite, kieselguhr (diatomaceous earth), expanded mica (vermiculite) and foam sand can be used. Depending on the application, the proportion of fillers in mortar or concrete can usually be between 0 and 80% by weight, based on the total weight of the mortar or concrete.
  • Suitable additives are generally known flow agents, defoamers, water retention agents, pigments, fibers, dispersion powders, wetting agents, retarders, accelerators, complexing agents, aqueous dispersions and rheology modifiers.
  • the invention further relates to the use of zinc salts in Baustoffbindeschsystemen based on granulated slag to prevent discoloration. Preference is given to using zinc salts which have from 0 to 8 carbon atoms in their structure.
  • the present invention relates grouts or coatings containing the building material binder systems of the invention.
  • test specimen prisms with dimensions 4 ⁇ 4 ⁇ 16 cm are prepared from the mixed binder paste and stored in accordance with the said standard. This is followed by an obvious check for discoloration.
  • the mixtures M1 and M2 according to the invention are two-component mixtures, M3 is a one-component binder which is mixed with water as indicated.
  • the building material mixtures (M1 v to M3 v) marked V do not contain any zinc salts and are to be regarded as comparative examples.
  • the zinc salt-free samples of mixtures M1v. M2v and M3v are much darker to green-black in color. This discoloration occurs after mixing the mixtures and increases. The dark discoloration is retained even after a 28-day standard storage. In most cases, the discoloration is inhomogeneous, which particularly affects the visual impression.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention relates to construction material mixtures containing furnace slag and zinc salts comprising from 0 to 8 carbon atoms in the structure thereof. The invention further relates to the use of zinc salts for preventing discolorations during the curing of construction material mixtures.

Description

Die vorliegende Erfindung betrifft Baustoffbindemittelsysteme enthaltend Hüttensand als ein erstes Bindemittel sowie Mikrosilica und/oder Metakaolin als ein zweites Bindemittel, Zinksalze, wobei die Zinksalze von 0 bis 8 Kohlenstoffatome in ihrer Struktur aufweisen, sowie eine Alkalimetallverbindung als Aktivator. Weiterhin betrifft die Erfindung Fugenmörtel oder Beschichtungen, enthaltend die erfindungsgemäßen Baustoffbindemittelsysteme, sowie die Verwendung von Zinksalzen in Baustoffbindemittelsystemen auf Basis von Hüttensand zur Verhinderung von Verfärbungen.The present invention relates to building material binder systems containing granulated slag as a first binder and microsilica and / or metakaolin as a second binder, zinc salts wherein the zinc salts have from 0 to 8 carbon atoms in their structure, and an alkali metal compound as activator. Furthermore, the invention relates joint grout or coatings containing the building material binder systems according to the invention, and the use of zinc salts in building material binder systems based on granulated sludge to prevent discoloration.

Anorganische Bindemittelsysteme basierend auf reaktionsfähigen wasserunlöslichen Oxiden auf Basis von Siliziumdioxid in Verbindung mit Aluminiumoxid, die in wässrig alkalischem Medium aushärten, sind allgemein bekannt. Solche Bindemittelsysteme werden auch Geopolymere genannt und sind in EP 0 026 687 , EP 0 153 097 B1 und WO 82/00816 beschrieben.Inorganic binder systems based on reactive water-insoluble silica based oxides in conjunction with alumina which cure in aqueous alkaline medium are well known. Such binder systems are also called geopolymers and are in EP 0 026 687 . EP 0 153 097 B1 and WO 82/00816 described.

Als reaktionsfähiges Oxidgemisch kann dabei Metakaolin, Schlacke, Flugasche, aktivierter Ton oder eine Mischung daraus eingesetzt werden. Das alkalische Medium zur Aktivierung des Bindemittels besteht üblicherweise aus wässrigen Lösungen von Alkalikarbonaten, -Floriden und insbesondere Alkalihydroxid und/oder lösliches Wasserglas. Die erhärteten Bindemittel weisen dabei eine hohe mechanische und chemische Beständigkeit auf. Im Vergleich zu Zement sind diese kostengünstiger, beständiger und weisen eine günstigere CO2-Emissions-Bilanz auf.Metakaolin, slag, fly ash, activated clay or a mixture thereof can be used as a reactive oxide mixture. The alkaline medium for activating the binder usually consists of aqueous solutions of alkali metal carbonates, fluorides and in particular alkali metal hydroxide and / or soluble water glass. The hardened binders have a high mechanical and chemical resistance. Compared to cement, these are cheaper, more durable and have a more favorable CO 2 emission balance.

Hüttensand stellt eine reaktionsfähige Schlacke aus dem Hochofenprozess dar. Bindemittelsysteme auf Basis von Hüttensand als Hauptbestandteil der reaktiven Festkomponente in Verbindung mit einer wässrigen Lösung eines Alkalihydroxid und/oder Wasserglases können im Bauwesen durch Abmischung mit Füllern (Quarzsand mit entsprechender Körnung) und Additiven als Mörtel oder Betone zur Anwendung kommen. Beispielhaft sei hier die Verwendung in Fertigbauteilen, Beschichtungen und Fugenmörteln genannt.
Derartige Bindemittelsysteme und Mörtel werden in DE 3 133 503 , EP 1 236 702 , EP 1 081 114 , JP 2 302 346 , JP 4 012 043 und JP 11 079 822 beschrieben.Slag sand is a reactive slag from the blast furnace process. Binder systems based on slag sand as the main component of the reactive solid component in conjunction with an aqueous solution of an alkali hydroxide and / or water glass in construction by mixing with fillers (quartz sand with appropriate grain size) and additives as mortar or Concretes are used. By way of example, the use in prefabricated components, coatings and joint mortars may be mentioned here.
Such binder systems and mortars are in DE 3 133 503 . EP 1 236 702 . EP 1 081 114 . JP 2 302 346 . JP 4 012 043 and JP 11 079 822 described.

EP 1 236 702 A1 beschreibt eine Wasserglas enthaltende Baustoffmischung für die Herstellung von chemikalienbeständigen Mörteln auf Basis eines latent hydraulischen Bindemittels, Wasserglas sowie Metallsalz als Steuerungsmittel. Als latent hydraulischer Bestandteil kann dabei auch Hüttensand eingesetzt werden. Als Metallsalz werden Alkalisalze genannt und eingesetzt. EP 1 236 702 A1 describes a water glass-containing building material mixture for the production of chemical-resistant mortars based on a latent hydraulic binder, water glass and metal salt as a control agent. Granulated blastfurnace slag can also be used as a latent hydraulic component. As the metal salt alkali salts are called and used.

In der EP 0 457 516 A1 werden feuerfeste, wasserdichte, säurebeständige Binder aus Alkalisilikaten wie Mikrosilika beschrieben. In diesen Systemen werden verschiedene Metalloxide, darunter auch Zinkoxid als Abbindebeschleuniger eingesetzt.In the EP 0 457 516 A1 describes refractory, waterproof, acid-resistant binders of alkali metal silicates such as microsilica. In these systems, various metal oxides, including zinc oxide are used as setting accelerator.

Die CH 629 246 A5 beschreibt ein Verfahren zum Kleben einer Metallfolie auf eine Mineralfaserplatte, wobei ein Kleber aus Wasserglas, tonmineralischen Stoffen und unter anderem auch Oxiden der Erdalkalien oder des Zinks eingesetzt werden.The CH 629 246 A5 describes a method for adhering a metal foil to a mineral fiber board, wherein an adhesive of water glass, clay mineral substances and, inter alia, oxides of alkaline earths or zinc are used.

In der US 6 537 366 B1 werden Zusammensetzungen zum Färben von Beton beschrieben, welche wenigstens ein Derivat der Stearinsäure, ein Polymer und ein Pigment enthält. Als Stearinsäurederivat wird auch Zinkstearat aufgeführt. Die Stearinsäurederivate dienen als Hydrophobierungsmittel zur Verhinderung von Ausblühungen auf der Oberfläche von zementgebundenen Betonen. Die Schrift erwähnt nichts über die Effekte von zinkhaltigen Verbindungen als Mittel zur Verhinderung von Verfärbungen in hüttensandhaltigen Bindemittelsystemen.In the US Pat. No. 6,537,366 B1 For example, compositions for coloring concrete containing at least one derivative of stearic acid, a polymer and a pigment are described. As Stearinsäurederivat also zinc stearate is listed. The stearic acid derivatives serve as water repellents to prevent efflorescence on the surface of cementitious concretes. The document does not mention the effects of zinc-containing compounds as agents for preventing discoloration in slag-containing binder systems.

G. Qian, D.D. Sun, J.H. Tay beschreiben in "Characterization of mercury- and zincdoped alkali-activated slag matrix, Part II. Zinc", Cement and Concrete Research, Bd. 33, 2003, S. 1257 - 1258 , den Einfluss von Zn2+-Ionen auf eine alkali-aktivierte Hüttensandmatrix dahingehend, dass geringe Konzentrationen von Zn2+-Ionen nur einen geringen negativen Effekt bewirken. Größere Konzentrationen (2 %) wirken stark verzögernd. G. Qian, DD Sun, JH Tay describe in "Characterization of Mercury and Zinc Doped Alkali-activated Slag Matrix, Part II. Zinc", Cement and Concrete Research, Vol. 33, 2003, pp. 1257-1258 , the influence of Zn 2+ ions on an alkali-activated blastfurnace slag matrix in that low concentrations of Zn 2+ ions cause only a slight negative effect. Larger concentrations (2%) have a strong delay.

US 5 073 198 beschreibt ein verbessertes Verfahren zur Herstellung eines Baustoffmaterials, umfassend mit Portlandzement als Aktivator aktivierte Schlacke, eine saure Komponente und eine basische Komponente. Bei der sauren Komponente handelt es sich um Phosphat(e), bei der basischen Komponente um Magnesiumoxid in Kombination mit Oxiden wie z.B. Zinkoxid. Die Anwesenheit von Portlandzement erhöht die mechanische Festigkeit des Baustoffmaterials. US 5 073 198 describes an improved process for making a building material comprising slag activated with Portland cement activator, an acidic component and a basic component. The acidic component is phosphate (e), the basic component magnesium oxide in combination with oxides such as zinc oxide. The presence of Portland cement increases the mechanical strength of the building material.

Nachteilig bei den bekannten Baustoffmischungen auf Basis von alkalisch aktiviertem Hüttensand ist, dass es bei der Erhärtung des Systems zu Verfärbungen kommen kann. Insbesondere in Bereichen wo der Zutritt von Luftsauerstoff behindert ist zeigen sich verstärkt dunkle Verfärbungen. Es wird vermutet, dass diese Verfärbungen durch schwefelhaltige Verbindungen in der Oxidationsstufe -2 verursacht werden. Die mit diesem Bindemittelsystem hergestellten Mörtel und Betone zeigen somit kein einheitliches Farbbild. Insbesondere beim Einsatz solcher Bindemittelsysteme in sichtbaren Beschichtungen und Fugenmörteln können diese Verfärbungen zu nicht akzeptablen Ergebnissen führen.A disadvantage of the known building material mixtures based on alkaline activated slag sand is that it may cause discoloration when the system hardens. In particular, in areas where the access of atmospheric oxygen is hindered show increasingly dark discoloration. It is assumed that these discolorations are caused by sulfur-containing compounds in the oxidation state -2. The mortars and concretes produced with this binder system thus do not show a uniform color image. In particular, when using such binder systems in visible coatings and grout, these discolorations can lead to unacceptable results.

Aufgabe war es daher, ein Baustoffbindemittelsystem auf Basis von Hüttensand bereitzustellen, das nach Applikation und Aushärtung keine Verfärbungen zeigt.The task was therefore to provide a building material binder system based on granulated slag, which shows no discoloration after application and curing.

Diese Aufgabe wird mit den Merkmalen der unabhängigen Ansprüche gelöst.This object is achieved with the features of the independent claims.

Gegenstand der vorliegenden Erfindung ist demnach ein Baustoffbindemittelsystem enthaltend Hüttensand als ein erstes Bindemittel sowie Mikrosilica und/oder Metakaolin als ein zweites Bindemittel, dadurch gekennzeichnet, dass es Zinksalz enthält, wobei das Zinksalz von 0 bis 8 Kohlenstoffatome aufweist, sowie eine Alkalimetallverbindung als Aktivator.The present invention accordingly provides a building material binder system containing granulated slag as a first binder and microsilica and / or metakaolin as a second binder, characterized in that it contains zinc salt, wherein the zinc salt has from 0 to 8 carbon atoms, and an alkali metal compound as activator.

Besonders bevorzugt sind Zinksalze, welche keine Kohlenstoffatome in ihrer Struktur aufweisen. Bevorzugt enthalten ist mindestens ein in wässrig alkalischem Medium lösliches, organisches oder anorganisches Zinksalz, besonders bevorzugt anorganisches Zinksalz.Particularly preferred are zinc salts which have no carbon atoms in their structure. Preferably, at least one soluble in aqueous alkaline medium, organic or inorganic zinc salt, more preferably inorganic zinc salt.

Die erfindungsgemäßen Baustoffbindemittelsysteme bieten den Vorteil, dass sich mit ihnen kostengünstig verfärbungsfreie Mörtel und Betone, insbesondere Fugenmörtel und Beschichtungen für das Bauwesen, realisieren lassen.The building material binder systems according to the invention have the advantage that they can be used to inexpensively discolor mortar and concretes, in particular joint mortars and coatings for the construction industry.

Als Bindemittel können neben Hüttensand sowie Mikrosilica und/oder Metakaolin in den erfindungsgemäßen Baustoffbindemittelsystemen weitere bekannte Bindemittel eingesetzt werden. In Frage kommen beispielsweise Kaolin, Schlacke, Flugasche, aktivierter Ton, Siliziumoxide, Traß, Puzzolanerde, Kieselgur, Diatomeenerde, Gaize, Aluminiumoxide und/oder gemischte Aluminium/Siliziumoxide. Diese Stoffe sind auch unter den Oberbegriffen latente hydraulische Binder und Puzzolane bekannt. Dabei können eines oder mehrere der genannten Bindemittel mit Hüttensand zum Einsatz kommen. Besonders bevorzugt sind Flugaschen.In addition to granulated slag and microsilica and / or metakaolin, other known binders can be used as binders in the building-material binder systems according to the invention. In question, for example, kaolin, slag, fly ash, activated clay, silicon oxides, Traß, pozzolanic earth, diatomaceous earth, diatomaceous earth, Gaize, aluminum oxides and / or mixed aluminum / silicon oxides. These substances are also known by the generic terms latent hydraulic binders and pozzolans. In this case, one or more of said binders can be used with granulated blastfurnace slag. Fly ash is especially preferred.

Bei Hüttensand handelt es sich um granulierte Hochofenschlacke. Feingemahlener granulierter Hüttensand wird auch als Hüttensandmehl bezeichnet. Derartige Produkte sind dem Fachmann als Bindemittel allgemein bekannt. Hüttensandmehl variiert, je nach dessen Herkunft und seiner Aufbereitungsform, in seiner Mahlfeinheit und Korngrößenverteilung, wobei die Mahlfeinheit Einfluss auf die Reaktivität des Hüttensandmehls hat. Als Kenngröße für die Mahlfeinheit wird der Blainewert herangezogen. Der Hüttensand, bzw. Hüttensandmehl kann allgemein für durch alkalische Aktivierung abbindende Baustoffmischungen in bekannter Form eingesetzt werden. Bevorzugt ist Hüttensand, der einen Blainewert von größer 2000 cm2/g, besonders bevorzugt größer 3000 cm2/g aufweist. Insbesondere kommt Hüttensand in Frage, der einen Blainewert zwischen 2000 bis 10000 cm2/g, insbesondere bevorzugt zwischen 3000 und 5000 cm2/g aufweist. Besonders bevorzugt gemäß der vorliegenden Erfindung ist Hüttensand, der zwischen 30 und 45 Gew.-% CaO, zwischen 30 und 45 Gew.-% SiO2, zwischen 5 und 15 Gew.-% Al2O3 und zwischen 4 und 17 Gew.-% MgO enthält.Slag sand is granulated blast furnace slag. Finely ground granulated blastfurnace slag is also known as blastfurnace slag. Such products are generally known to the skilled person as a binder. Granulated blastfurnace flour varies in its fineness and particle size distribution, depending on its origin and its form of preparation, whereby the fineness of grinding has an influence on the reactivity of the granulated blastfurnace meal. As a parameter for the fineness of the Blainewert is used. The blastfurnace slag or blastfurnace sludge can generally be used in a known form for building material mixtures which set by alkaline activation. Preference is given to granulated slag which has a Blaine value of greater than 2000 cm 2 / g, particularly preferably greater than 3000 cm 2 / g. In particular, blast furnace slag comes into question, which has a Blaine value between 2000 to 10000 cm 2 / g, particularly preferably between 3000 and 5000 cm 2 / g. Particularly preferred according to the present invention is blast furnace slag containing between 30 and 45% by weight of CaO, between 30 and 45% by weight of SiO 2 , between 5 and 15% by weight Al 2 O 3 and between 4 and 17% by weight. - contains% MgO.

Das erfindungsgemäße Baustoffbindemittelsystem enthält als Aktivator vorzugsweise pulverförmigen Aktivator, besonders bevorzugt Alkalimetallhydroxid, Alkalimetallsilikat, insbesondere alkalisches Kaliwasserglas, Alkalimetallaluminat, Alkalimetallcarbonat und/oder Alkalimetallsulfate. Allgemein handelt es sich beim Alkalimetall um Natrium, Kalium oder Lithium.The building material binder system according to the invention contains as activator preferably pulverulent activator, particularly preferably alkali metal hydroxide, alkali metal silicate, in particular alkaline potassium silicate, alkali metal aluminate, alkali metal carbonate and / or alkali metal sulfates. Generally, the alkali metal is sodium, potassium or lithium.

Das Alkalimetallsilikat kann Na-, K- oder Lithiumwasserglas sein, bevorzugt Kaliwasserglas. Das Modul (Mol-Verhältnis SiO2 zu Alkalioxid) des Wasserglases beträgt vorzugsweise kleiner 4, besonders bevorzugt kleiner 2. Im Fall von Wasserglaspulver beträgt das Modul zweckmäßig kleiner als 5, bevorzugt zwischen 1 und 4, besonders bevorzugt zwischen 1 und 3. Bei der oben genannten Alkalimetallverbindung als Aktivator kann es sich auch um Natrium-, Kalium- und Lithiumhydroxid handeln.The alkali metal silicate may be sodium, potassium or lithium waterglass, preferably potassium silicate glass. The modulus (molar ratio SiO 2 to alkali oxide) of the water glass is preferably less than 4, particularly preferably less than 2. In the case of water glass powder, the modulus is expediently less than 5, preferably between 1 and 4, particularly preferably between 1 and 3. In the case of The above-mentioned alkali metal compound as an activator may also be sodium, potassium and lithium hydroxide.

Des Weiteren enthält das erfindungsgemäße Baustoffbindemittelsystem die folgenden Komponenten vorzugsweise in folgenden Anteilen: zwischen 0,001 und 10 Gew.-% Zinksalz, zwischen 5 und 50 Gew.-% Hüttensand, zwischen 5 und 50 Gew.-% Aktivator, wobei die Gewichtsangaben jeweils bezogen sind auf das Gesamtgewicht des Baustoffbindemittelsystems.Furthermore, the building material binder system according to the invention preferably contains the following components in the following proportions: between 0.001 and 10% by weight of zinc salt, between 5 and 50% by weight of granulated slag, between 5 and 50% by weight of activator, the weight data being based in each case on the total weight of the building material binder system.

Als erfindungsgemäßes Zinksalz können unter der Voraussetzung, dass das Zinksalz von 0 bis 8 Kohlenstoffatome in seiner Struktur aufweist in den Mischungen allgemein bekannte Verbindungen eingesetzt werden, beispielsweise organische (beispielsweise Zinksalze organischer Carbonsäuren) oder anorganische Zinksalze, bevorzugt auf der Basis von Zn2+, besonders bevorzugt anorganische Zinksalze, insbesondere anorganische Zinksalze, die in wässrigem alkalischem Medium löslich sind. Bevorzugt werden als Zinksalz Zinkoxid, Zinkfluorid und/oder Zinksulfat eingesetzt. Auch Zinkchlorid kann eingesetzt werden, ist aber wegen seines Chloridgehalts in größeren Mengen weniger erwünscht. Insbesondere bevorzugt wird Zinkoxid eingesetzt, welches in wässriger alkalischer Lösung gut löslich ist.As the zinc salt according to the invention, it is possible, provided that the zinc salt has from 0 to 8 carbon atoms in its structure, to use mixtures which are generally known in the mixtures, for example organic (for example zinc salts of organic carboxylic acids) or inorganic zinc salts, preferably those based on Zn 2+ , particularly preferred inorganic zinc salts, in particular inorganic zinc salts, which are soluble in an aqueous alkaline medium. Zinc oxide, zinc fluoride and / or zinc sulfate are preferably used as the zinc salt. Zinc chloride can also be used, but is less desirable because of its chloride content in larger quantities. Zinc oxide is particularly preferably used, which is readily soluble in aqueous alkaline solution.

Besonders bevorzugt sind im Baustoffbindemittelsystem 0,1 bis 7 Gew.-% und insbesondere 0,5 bis 5 Gew.-% Zinksalz enthalten. Zinksalze mit mehr als acht Kohlenstoffatomen pro Struktureinheit, wie zum Beispiel Zinkstearat, weisen den Nachteil auf, dass vermutlich aufgrund ihrer hydrophoben Struktur die Festigkeiten der Baustoffmischungen negativ beeinflusst werden. Auch wird das erhärtete Baustoffmaterial poröser und damit weniger haltbar. Es ist grundsätzlich möglich die genannten Zinksalze alleine oder Mischungen von verschiedenen Zinksalzen zu verwenden.In the building material binder system it is particularly preferred to contain from 0.1 to 7% by weight and in particular from 0.5 to 5% by weight of zinc salt. Zinc salts with more than eight carbon atoms per structural unit, such as zinc stearate, have the disadvantage that probably due to their hydrophobic structure, the strength of the building material mixtures are adversely affected. Also, the hardened building material becomes more porous and thus less durable. It is basically possible to use the said zinc salts alone or mixtures of different zinc salts.

Die erfindungsgemäßen Zinksalze können bevorzugt in Pulverform in die Hüttensandmehl enthaltende Mischung eingemischt werden. Bevorzugt wird das Zinksalz in die pulverförmige hüttensandhaltige Bindemittelmischung untergemischt.The zinc salts according to the invention can preferably be mixed into the mixture containing the granulated blastfurnace meal in powder form. Preferably, the zinc salt is mixed into the powdery granulated slag-containing binder mixture.

Es ist auch möglich die Zinksalze als Lösung in einem vorstehend beschriebenen Aktivator einzusetzen. Vor dem Anmischen des Bindemittels mit der wässrigen Aktivatorlösung kann dabei bevorzugt das Zinksalz in der wässrigen Aktivatorlösung aufgelöst werden.It is also possible to use the zinc salts as a solution in an activator described above. Before mixing the binder with the aqueous activator solution, the zinc salt may preferably be dissolved in the aqueous activator solution.

Beim Zinksalz handelt es sich vorzugsweise um ein gemahlenes Salz, welches bevorzugt Körngrößen mit einem d90-Wert kleiner 90 µm aufweist. Die Lösungsgeschwindigkeit des Zinksalzes erhöht sich mit steigender Mahlfeinheit.The zinc salt is preferably a ground salt, which preferably has particle sizes with a d 90 value of less than 90 μm. The rate of dissolution of the zinc salt increases with increasing fineness of fining.

Bevorzugt ist der vorstehend beschriebene Aktivator pulverförmig. Man spricht in diesem Fall von einem Einkomponentensystem, welches dann durch die Zugabe von Wasser zum Erhärten gebracht werden kann. Der Aktivator dient der Beschleunigung des Abbindeprozesses der Bindemittel.The activator described above is preferably pulverulent. This is referred to as a one-component system, which can then be made to harden by the addition of water. The activator serves to accelerate the setting process of the binders.

Der Aktivator kann auch in Form einer Lösung zum Einsatz kommen. In diesem Fall wird üblicherweise die Aktivatorlösung mit einer Mischung aus Hüttensandmehl und den weiteren Bindemitteln vermischt, worauf das Aushärten einsetzt..The activator can also be used in the form of a solution. In this case, usually the activator solution is mixed with a mixture of granulated blastfurnace and the other binders, whereupon curing begins.

Gegebenenfalls können zwischen 0 und 80 Gew.-%, besonders bevorzugt zwischen 30 und 70 Gew.-% Füllstoffe, und gegebenenfalls zwischen 0 und 15 Gew.-% sich von den vorstehend genannten Komponenten unterscheidende Additive im Baustoffbindemittelsystem enthalten sein. Die Gewichtsangaben sind jeweils bezogen auf das Gesamtgewicht des Baustoffbindemittelsystems.Optionally, between 0 and 80% by weight, particularly preferably between 30 and 70% by weight of fillers, and optionally between 0 and 15% by weight, of additives differing from the abovementioned components may be present in the building material binder system. The weights are in each case based on the total weight of the building material binder system.

Das erfindungsgemäße Baustoffbindemittelsystem wird vorzugsweise zur Herstellung von Mörteln und Betonen verwendet. Zur Herstellung solcher Mörtel und Betone wird das Baustoffbindemittelsystem üblicherweise mit weiteren Komponenten wie Füllstoffen, latent hydraulischen Stoffen und weiteren Additiven, gemischt. Die Zugabe des pulverförmigen Aktivators erfolgt dabei bevorzugt bevor die genannten Komponenten mit Wasser angemischt werden, sodass ein sogenannter Werktrockenmörtel hergestellt wird. So liegt die Aktivierungskomponente in pulverförmiger Form, bevorzugt als Mischung mit den Bindemitteln und/oder Sand vor. Alternativ kann eine wässrige, bevorzugt alkalische Aktivierungslösung zu den anderen pulverförmigen Komponenten zugegeben werden. In diesem Fall spricht man dann von einem zweikomponentigen Bindemittel.The building material binder system according to the invention is preferably used for the production of mortars and concretes. For the preparation of such mortars and concretes, the building material binder system is usually mixed with other components such as fillers, latent hydraulic substances and other additives. The addition of the powdered activator is preferably carried out before the said components are mixed with water, so that a so-called dry mortar is prepared. Thus, the activation component is in powder form, preferably as a mixture with the binders and / or sand. Alternatively, an aqueous, preferably alkaline, activating solution may be added to the other powdered components. In this case one speaks then of a two-component binder.

Als Füllstoff kommen allgemein bekannte Kiese, Sande und/oder Mehle in Frage, beispielsweise auf der Basis von Quarz, Kalkstein, Schwerspat oder Tone. Auch Leichtfüllstoffe wie Perlite, Kieselgur (Diatomeenerde), Blähglimmer (Vermiculit) und Schaumsand können verwendet werden. Der Anteil der Füllstoffe im Mörtel oder Beton kann dabei üblicherweise je nach Anwendung zwischen 0 und 80 Gew.-% bezogen auf das Gesamtgewicht des Mörtels oder Betons betragen.Suitable fillers are generally known gravels, sands and / or flours, for example based on quartz, limestone, barite or clays. Also light fillers such as perlite, kieselguhr (diatomaceous earth), expanded mica (vermiculite) and foam sand can be used. Depending on the application, the proportion of fillers in mortar or concrete can usually be between 0 and 80% by weight, based on the total weight of the mortar or concrete.

Als Additive kommen allgemein bekannte Fließmittel, Entschäumer, Wasserretentionsmittel, Pigmente, Fasern, Dispersionspulver, Netzmittel, Verzögerer, Beschleuniger, Komplexbildner, wässrige Dispersionen und Rheologiemodifizierer in Betracht.Suitable additives are generally known flow agents, defoamers, water retention agents, pigments, fibers, dispersion powders, wetting agents, retarders, accelerators, complexing agents, aqueous dispersions and rheology modifiers.

Die Erfindung betrifft weiterhin die Verwendung von Zinksalzen in Baustoffbindemittelsystemen auf Basis von Hüttensand zur Verhinderung von Verfärbungen. Bevorzugt werden dabei Zinksalze verwendet, die von 0 bis 8 Kohlenstoffatome in ihrer Struktur aufweisen.The invention further relates to the use of zinc salts in Baustoffbindemittelsystemen based on granulated slag to prevent discoloration. Preference is given to using zinc salts which have from 0 to 8 carbon atoms in their structure.

Weiterhin betrifft die vorliegende Erfindung Fugenmörtel oder Beschichtungen, welche die erfindungsgemäßen Baustoffbindemittelsysteme enthalten.Furthermore, the present invention relates grouts or coatings containing the building material binder systems of the invention.

Beispiele:Examples: Herstellung des Bindemittelleims:Preparation of the binder lime:

Zuerst werden alle pulverförmigen Bestandteile vorgemischt und dann mit Wasser bzw. wie bei M1, M2, M1v, M2v mit der flüssigen Aktivierungskomponente in Anlehnung an DIN EN 196 zu einem homogenen Bindemittelleim gerührt.First, all the powdery constituents are premixed and then stirred with water or as in M1, M2, M1v, M2v with the liquid activation component in accordance with DIN EN 196 to form a homogeneous binder.

Herstellung der Probekörper:Preparation of specimens:

Aus dem angerührten Bindemittelleim werden laut DIN EN 196 Probekörperprismen mit den Massen 4 x 4 x 16 cm hergestellt und in Anlehnung an die genannte Norm gelagert. Anschliessend erfolgt eine augenscheinliche Prüfung auf Verfärbungen.According to DIN EN 196 test specimen prisms with dimensions 4 × 4 × 16 cm are prepared from the mixed binder paste and stored in accordance with the said standard. This is followed by an obvious check for discoloration.

Die Beispielrezepturen sind in untenstehender Tabelle zusammengefasst.

Figure imgb0001
The example formulations are summarized in the table below.
Figure imgb0001

Die erfindungsgemäßen Mischungen M1 und M2 sind zweikomponentige Mischungen, bei M3 handelt es sich um ein einkomponentiges Bindemittel, das mit Wasser wie angegeben angemischt wird. Die mit V gekennzeichneten Baustoffmischungen (M1 v bis M3 v) enthalten keine Zinksalze und sind als Vergleichsbeispiele zu betrachten.The mixtures M1 and M2 according to the invention are two-component mixtures, M3 is a one-component binder which is mixed with water as indicated. The building material mixtures (M1 v to M3 v) marked V do not contain any zinc salts and are to be regarded as comparative examples.

Bereits nach 24 Stunden stellt man bei der augenscheinlichen Prüfung deutlich fest, dass die zinksalzhaltigen Proben M1 (zementgrau), M2 (beige bis sandfarben) und M3 (hellgrau) keine dunklen Verfärbungen zeigen. Das Farbbild der Baustoffmassen erscheint einheitlich.After only 24 hours, the apparent test clearly shows that the samples containing zinc salt M1 (cement gray), M2 (beige to sand color) and M3 (light gray) show no dark discoloration. The color image of the building materials appears uniform.

Die zinksalzfreien Proben der Mischungen M1v. M2v und M3v dagegen sind wesentlich dunkler bis grünschwarz verfärbt. Diese Verfärbung tritt nach dem Anrühren der Mischungen auf und verstärkt sich. Die dunklen Verfärbungen bleiben auch nach einer 28-tägigen Normlagerung erhalten. Meistens sind die Verfärbungen inhomogen, was den optischen Eindruck besonders beeinträchtigt.The zinc salt-free samples of mixtures M1v. M2v and M3v, on the other hand, are much darker to green-black in color. This discoloration occurs after mixing the mixtures and increases. The dark discoloration is retained even after a 28-day standard storage. In most cases, the discoloration is inhomogeneous, which particularly affects the visual impression.

Claims (9)

  1. Building material binder system containing slag sand as a first binder and microsilica and/or metakaolin as a second binder, characterized in that it contains a zinc salt, the zinc salt having from 0 to 8 carbon atoms, and an alkali metal compound as an activator.
  2. Building material binder system according to Claim 1, characterized in that it contains fly ashes as a further binder.
  3. Building material binder system according to either of Claims 1 and 2, characterized in that the slag sand has a specific surface area (Blaine value) of greater than 2000 cm2/g.
  4. Building material binder system according to any of Claims 1 to 3, characterized in that it contains a pulverulent activator.
  5. Building material binder system according to any of Claims 1 to 4, characterized in that it contains alkali metal hydroxide, alkali metal silicate, preferably alkaline potassium waterglass, alkali metal aluminate, alkali metal carbonate and/or alkali metal sulphates as the activator.
  6. Building material binder system according to any of Claims 1 to 5, characterized in that it contains the following components:
    between 0.001 and 10% by weight of zinc salt,
    between 5 and 50% by weight of slag sand,
    between 5 and 50% by weight of activator,
    the weight data being based in each case on the total weight of the building material binder system.
  7. Building material binder system according to any of Claims 1 to 6, characterized in that it contains zinc oxide, zinc fluoride and/or zinc sulphate as the zinc salt.
  8. Use of zinc salts having from 0 to 8 carbon atoms in a building material binder system according to any of Claims 1 to 7 for preventing discolorations.
  9. Jointing mortars or coatings containing a building material binder system according to any of Claims 1 to 7.
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CN115443256A (en) * 2020-05-15 2022-12-06 喜利得股份公司 Fine-ground granulated blast furnace slag in cementitious multicomponent mortar systems for use as inorganic chemical fastening systems

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AU2009253285B2 (en) 2014-10-09
DK2297061T3 (en) 2012-12-03
US20110100262A1 (en) 2011-05-05
JP5460700B2 (en) 2014-04-02
PL2297061T3 (en) 2013-01-31
EP2297061A1 (en) 2011-03-23
ES2390817T3 (en) 2012-11-16
JP2011527277A (en) 2011-10-27
CA2725585A1 (en) 2009-12-03
CA2725585C (en) 2016-03-15
CN102046559B (en) 2013-06-26
AU2009253285A1 (en) 2009-12-03
CN102046559A (en) 2011-05-04
WO2009144141A1 (en) 2009-12-03
US8118931B2 (en) 2012-02-21

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